Process for preparing halogencontaining polyolefins



United States Patent PROCESS FOR PREPARING HALOGEN- CONTAINING PQLYOLEFINS Erich Heitzer, Hofheim (Taunus), Albert Gustav Martin Gumboldt, Frankfurt am Main, Giinter Messwarb, ,Kelkheim (Taunus), and Gerhard Bier, Frankfurt am Main, Germany, assignors to Farbwerke Hoechst Aktiengesellschaft vol-male Meister Lucius & Briining, Frankfurt am Main, Germany, a corporation of Germany No Drawing. Application November 20, 1956 Serial No. 623,310

Claims priority, application Germany November 23, 1955 7 Claims. (Cl. 260-943) When the process for polymerizing lower olefins, especially ethylene, had been discovered, the halogenation products of these compounds, particularly the chlorine and bromine derivatives, were also prepared. Thus, for example, solid, high-molecular polyethylene prepared by the high-pressure process can be converted, in solvents which themselves do not react with chlorine, and with or without the use of pressure, into products of high chlorine content. Suitable solvents or dispersing agents for this punposea-re carbon tetrachloride, chloroform, and glacial acetic acid or their mixtures. The best suited is carbon tetrachloride. "If solvents that contain hydrogen atoms are used, it must be expected that they Will be chlorinated ogether with the m r molecules. High-boiling solvents with boiling points above 200 C. are less suita le for this type of reaction because they are hard to remove. The chlorination temperature may .vary over Wide limits. The chlorination process may be conducted with or without pressure and with the use of light of short wave length, such as is produced by the mercury vapor lamp or the carbon arc lamp. Halogenations have also been carried out in water as a dispersing agent, but the products obtained are usually of lower halogen content than those prepared in organic solvents. Moreover, the absorption of halogen is slower. .Sulfuryl chlorid oo, a e n u ed a a qr a n agent vfor polymeric ethylene in conjunction with ultraviolet light. Valuable synthetics of elastic vrubherliloe properties may be prepared by sulfochlorinating (simultaneously treating .With chlo ne and sul l l dioxide) p ye hy The known processes f P p ng a o e ontai ng polyolefins re er t po yme s p pa by p ym r i und r h P s ure The discovery of processes of polymerizing lower olefins at low pressures in the presence of salts of the IVb, Yb and VIb groups of elements of the periodic system and organoaluminum compounds as catalysts in accordance with Belg an Patents 540,459, 533,362, 534,792, nd 534,888 resulted in the possibility of preparing, by varying the catalyst system, polymers of widely-varyingmo- Lecular weight.

,Ihe dispersing agents used in these processes are hydrocarbons. When polyolefins are prepared by these processes and subsequently halogenated ,or sulfochlorihated th p lymer mu t b tran fi om he yd sas es pha i o a phas f xa p in ca bo tet ah sride; whi h is su tab e for h los n tion and s l chlorination. This transfer from .oneorganic phase into anothe c eams Ph se is n veni and exp n 'It has nowbeen found that halogen-containing, as well .lsa qeena ,s lfiu ccn ain ns po yolefins. o g y useful properties are prepared by halogenating or sulfo- 2,906,743 Patented Sept. 29, 1959 halogenating polyolefins in a halogen resisting dispersing medium in which polymerization of the olefins to polyolefins can be carried out in the presence of a catalytic mixture of a salt of an element selected from groups 1%, Vb and VIb of the periodic system and an organoaluminum compound with a halogen carrier selected from the "group consisting of elementary halogen and a combination of a halogen and sulfur dioxide.

It has been found that the process is particularly useful when carried out on polyolefins prepared according to US. Serial No. 603,886, filed August 14, 1956 and German patent application F 18,866, filed November 18, 1955, by carrying out the halogenation process on the polymerization reaction mixture'without-isolation of the polymer prior to the halogenating treatment with halogen or a combination of halogen and sulfur dioxide. In this anne th am h l ns in d spe s n med um c n be e f th he p lymer n an l genation or sulfohalogenation. It is especially advantageous to carry o the ch or nat o or ul e u hlorinat o and sulfochlorination in accordance with this process.

. T e p e re i p r a nts ar al gen-stable agents, e.g., carbon tetrachloride. With the use of C61,, low-molecular solid polymers are, under certain conditions, formed during-the polymerization period. When fluerin and c r ea n co p un s. the i n point of which is advantageously below 200 C., are used as solvents, e.g., CF Cl. CF Cl or CFCl .CF Cl, the products that are obtained are more highly molecular and, under certain conditions, more homogeneous than t ose prepared with the us of C 4- n es persion media have certain advantages in the preparation of h lecul r po e n because t ey are e di y removed after the halogenationas a result .of their lower boiling point.

. Halogenation or sulfohalogenation can be carried out without pressure or at higher temperatures and under pressure,-e.g., SO- C. at 1-30 atmospheres pressure with or without the action of light of short-wave length, and with or without the action of the known halogen transfer agents, e.g., ferric chloride, aluminum chloride, acetone peroxide, etc. This mode of operation in the same solvent constitutes a great technical simplification of the halogenation process. A further advantage of the process in accordance with the invention is that the salts of elements of groups IVb, Vb and VIb of the periodic system and the organoaluminumcompounds used as polymeli iq at ly t a c n e int ha og sa ts a the beginning Of the halogenation process and then function as effective halogen transfer agents.

Especially suitable for this process, i. e., polymerization and halogenation or sulfochlorination in the same reaction medium, are unsaturated hydrocarbons having terminal double bonds, e.g., ethylene, propylene-isobutylene, l-butenc, l-hexene, l-octene, styrene, ,a-methylstyrene nuclearly alkylated styrene, etc.

The Working-up of dispersions and/or solutions of the halogen-containing polymers is conducted in the usual manner by expelling thesolvent or dispersing agent under vacuum, or with the ,aid of steam, or by precipitation with precipitating agentssuch as methanol. 'It is advantageous to add acid acceptors, e. g., soda, in the workingup process.

The resulting halogenated polymers are recovered ;by centrifugation or suction filtration.

The remaining halogen-containing polymers which, depending on the degree of halogenation or on the degree of polymerization of the polymer, are soft rubbery and .e sst te he d a d sil en masses whic a su ble plasticizers, textile assistants, raw materials for lacquers, and synthetics.

I The invention is illustrated in the following examples:

Example 1 Polymeric propylene having an average degree of polymerization of 22, as it occurs in carbon tetrachloride after polymerization admixed with titanium salts and organoaluminum compounds in the form of a 33% solution, is chlorinated for 13 hours at the boiling point of .CCl, with the use of a reflux condenser, and with stirring and ultraviolet radiation. The viscous solution is added dropwise to boiling water, the CCL, is distilled, and there remains a solid, white foam which is subsequently ground in a mill with methanol and water. A fine, white powder having a chlorine content of 70.1% is obtained.

Example 2 Example 3 Polymeric ethylene having an average degree of poly merization of 28, as prepared by polymerization with titanium salts and organoaluminum compounds in accordance with U. S. application Serial No. 603,886, filed August 14, 1956, and German patent application F 18,866, filed November 18, 1955, in the form of a 25% solution in carbon tetrachloride boiling at 7677 C., is chlorinated for 15 hours at the boiling point of the solvent. During the chlorination the solution is irradi ated with light from a mercury vapor lamp. The solution is added to boiling water and the carbon tetrachloride evaporated. The solid residue is worked up as described in Example 1. Chlorine content of product=59.5%.

Example 4 Polymeric propylene as it occurs in carbon tetrachloride after polymerization with titanium salts and organoaluminum compounds in the form of a 10% solution is treated slowly with bromine at the boiling point of CCL; and under ultraviolet radiation. One mole bro- 'mine is used per polymer unit (1 atom bromine volatilizes as HBr). The reaction product is decanted into double its volume of methanol and separated from the precipitated bromine product by suction filtration. After 'reprecipitation the bromine content is 65.7%.

Example 5 A 25% solution of the polymer obtained by polymerizing propylene in carbon tetrachloride is treated at the boiling point of carbon tetrachloride with a mixture of one part chlorine and three parts sulfur dioxide under ultraviolet radiation. The reaction product is added to double its volume of isopropyl alcohol; the precipitated sulfochlorinated polypropylene is separated and washed with isopropyl alcohol. Chlorine content=49.5%; sulfur content=4.1%.

Example 6 Chlorine is introduced at 400 C. into two liters of an about 5% trichlorotrifluoroethane dispersion of polyethylene as obtained by polymerization with the use of titanium tetrachloride and triethylalurninum (see Example 2). After 15 minutes a sample of filtered polyethylene taken from the chlorination mixture has a chlorine content of 5%.

Example 7 To a. solution of 4.5 cc. aluminum ethyl sequichloride in 475 cc. of 1,1,2,2-tetrachloroethane is added dropwise while stirring and adding ethylene 1.0 cc. TiCl in 25 cc. af tetrachloroethane. After addition of the TiCl the mixed catalyst system was cooled to -15 C. and ethylene addition is continued at the rate of 50 liters per hour while gradually adding a 16% solution of aluminum ethyl sesquichloride. At the end of 7 hours the polymerization is stopped by interrupting the flow of ethylene. To this reaction mixture is then added a stream of gaseous chlorine with temperature control to maintaina temperature not exceeding C. At the end of 16 hours a chlorinated polyethylene of chlorine content of about 60% chlorine is obtained.

Example 8 Example 7, when repeated using C Cl F as the dispersing medium for the polymerization and subsequently as the chlorination solvent, gives similar results. However, the chlorinated polyethylene has a higher viscosity.

What is claimed is:

1. An improved process for the preparation of a halo genated polyolefin which comprises contacting an olefin selected from the group consisting of ethylene and propylene with a catalytic amount of a catalyst mixture of a titanium salt and an aluminum alkyl compound selected from the group consisting of aluminum trialkyl and aluminum alkyl sesquihalide, dispersed in a halogen-inert halogenated aliphatic liquid, to produce a reaction mixture containing a polymer of said olefin, contacting said reaction mixture with a halogenating agent selected from the group consisting of chlorine, bromine, and a mixture of chlorine and S0 at a temperature of from about 40 C. and at a pressure of up to about 30 atmospheres, whereby the aforesaid catalyst components are converted into halogen transfer agents, and recovering a halogenated polyolefin, thus employing the same halogen'inert dispersing medium for both the polymerization and the subsequent halogenation.

2. An improved process for the preparation of a halogenated polyolefin which comprises contacting an olefin selected from the group consisting of ethylene and propylene with a catalytic amount of a catalyst mixture of TiCl and an aluminum alkyl compound selected from the group consisting of aluminum trialkyl and aluminum alkyl sesquihalide, dispersed in a halogen-inert halogenated aliphatic liquid, to produce a reaction mixture containing a polymer of said olefin, contacting said reaction mixture with a halogenating agent selected from the group consisting of chlorine, bromine, and a mixture of chlorine and S0 at a temperature of from about 40- 150" C. and at a pressure of up to about 30 atmospheres, whereby the aforesaid catalyst components are converted into halogen transfer agents, and recovering a halogenated polyolefin, thus employing the same halogen-inert dispersing medium for both the polymerization and the subsequent halogenation.

3. The process of claim 2 wherein said reaction mixture containing said polymer is contacted with chlorine.

'is carbon tetrachloride.

7. The process of claim 2 wherein said organic liquid 5 contains fluorine and chlorine substituents and boils at a 2,695,899 temperature below 200 C. 2,748,105 2,825,723 References Cited in the file of this patent UNITED STATES PATENTS 5 2,503,252 Ernsberger Apr. 11, 1950 6 Becker et a1 Nov. 30, 1954 Becker et a1 May 29, 1956 Ballauf et a1 Mar. 4, 1958 FOREIGN PATENTS Belgium May 16, 1955 

1. AN IMPROVED PROCESS FOR THE PREPARATION OF A HALOGENATED POLYOLEFIN WHICH COMPRISE CONTACTING AN OLEFIN SELECTED FROM THE GROUP CONSISTING OF ETHYLENE AND PROPYLENE WITH A CATALYST AMOUNT OF A CATALYST MIXTURE OF A TITANIUM SALT AND AN ALUMINIUM ALKYL COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALUMINIUM TRIALKYL ALUMINUM ALKYL SESQUIHALIDE, DISPERSED IN A HALOGEN-INERT HALOGENATED ALIPHATIC LIQUID, TO PRODUCE A REACTION MIXTURE CONTAINING A POLYMER OF SAID OLEFIN, CONTACTING SAID REACTION MIXTURE WITH A HALOGENATING AGENT SELECTED FROM THE GROUP CONSISTING OF CHLORINE, BROMINE, AND A MIXTURE OF CHLORINE AND SO2 AT A TEMPERATURE OF FROM ABOUT 40150* C, AND A PRESSURE OF UP TP ABOUT 30 ATMOSPHERES, WHEREBY THE AFORESAID CATALYST COMPONENTS ARE CONVERTED INTO HALOGEN TRANSFER AGENTS, AND RECOVERING A HALOGENATED POLYOLEFIN, THUS EMPLOYING THE SAME HALOGEN-INERT DISPERSING MEDIUM FOR BOTH THE POLYMERIZATION AND THE SUBSEQUENT HALOGENATION. 